Gelling compositions comprising optically enriched gellants

ABSTRACT

The subject invention relates to low-aqueous gelling compositions comprising optically enriched gellants having the structure: ##STR1## wherein A and B independently represent alkyl groups such that the gellant is an asymmetric, di-chiral, di-hydroxy fatty acid that is about 90% or more in the R, R or S, S form and has from about 6 to about 30 carbon atoms.

This is a division of application Ser. No. 08/286,997, filed on Aug. 8,1994, U.S. Pat. No. 5,607,972.

FIELD OF THE INVENTION

The subject invention relates to low-aqueous gelling compositions.

BACKGROUND OF THE INVENTION

Organic cosmetic products with different hardness and rheologicalproperties can be achieved by varying the ratio of waxy and/or pastyoils to liquid organic oils in a given composition. In general, thesecosmetic products provide good skin feel, but are limited in the amountof liquid oil that can be formulated. These products can also leavevisible residue on the skin.

Gels have the ability to retain increased mounts of liquid in a cosmeticcomposition while significantly reducing or eliminating the visibleresidue on the skin as compared to a waxy cosmetic of equal hardness.However, one significant disadvantage of typical gel compositions is atendency of the liquid material to escape or leak from the gel network.This leaking of the liquid material can result in poor gel formation andlower gel stability of any gel which is formed. The leaking may alsocause processing difficulties at the temperatures and holding timestypically encountered during manufacture.

It is an object of the subject invention to provide low-aqueous gellingcompositions with superior gel formation.

SUMMARY OF THE INVENTION

The subject invention involves gelling compositions comprising opticallyenriched, asymmetric, di-chiral, di-hydroxy fatty acid gellants havingadjacent chiral centers.

DETAILED DESCRIPTION OF THE INVENTION

As used herein, the term "alkyl" means carbon-containing chains whichmay be straight, branched or cyclic; substituted or unsubstituted;saturated, monounsaturated (i.e., one double or triple bond in thecarbon chain), or polyunsaturated (i.e., two or more double bonds in thecarbon chain, two or more triple bonds in the carbon chain, one or moredouble and one or more triple bonds in the carbon chain). Unlessotherwise indicated, preferred alkyl are as follows. Preferred alkyl arestraight or branched chain, more preferably straight chain. Preferredalkyl are unsubstituted, or mono-, di-, or tri- substituted, morepreferably monosubstituted or unsubstituted, most preferablyunsubstituted. Preferred alkyl are C₆ to C₃₀, more preferably C₁₀ to C₂₈more preferably stiff C₁₄ to C₂₄ most preferably C₂₂.

As used herein, "substituted", in reference to alkyl groups, means suchgroups that can be mono- or polysubstituted. Preferred substituents areselected from the group consisting of halogen, hydroxy, amino, nitro,carboxy, thio, aryl, alkyl, alkoxy, and aryloxy. More preferredsubstituents include alkyl, alkoxy and aryl.

As used herein, the term "aryl" means aromatic rings which may beunsubstituted or substituted. Preferred aryl are phenyl or naphthyl,especially phenyl. Preferred aryl are mono-, di- or tri-substituted, orunsubstituted; more preferred aryl are monosubstituted or unsubstituted.Preferred aryl substitutents include alkyl, halo, amino, hydroxy,alkoxy, cyano, nitro and trifluoromethyl.

As used herein, the term "alkoxy" means O-alkyl.

As used herein, the term "aryloxy" means O-aryl.

Gelling Agent

The subject compositions comprise optically enriched gelling agents. Thesubject gelling agents are asymmetric, linear, branched or cyclic,substituted or unsubstituted, di-chiral, di-hydroxy fatty adds havingthe structure: ##STR2## wherein A and B each represent linear, branchedor cyclic, saturated or unsaturated, substituted or unsubstituted alkylhaving from about 1 to about 13 carbon atoms, preferably from about 3 toabout 12 carbon atoms, more preferably from about 5 to about 10 carbonatoms; such that structure (I) represents a di-hydroxy fatty acid havingfrom about 6 to about 30 carbon atoms, more preferably from about 10 toabout 24, more preferably still from about 14 to about 22, mostpreferably about 18 carbon atoms. The two chiral centers in the subjectgellants lie in the carbon atoms substituted by the hydroxyl moieties.

Preferred gellants include 9,10-dihydroxystearic add,13,14-dihydroxystearic acid, 13,14-dihydroxydocosanoic add, and11,12-dihydroxystearic acid. The most preferred gellant is13,14-dihydroxydocosanoic acid.

As used herein, the term "optically enriched" means that the gellingagent contains about 90% or more, preferably about 95% or more, morepreferably 98% or more, most preferably about 100% of a givenstereoisomer (i.e. intramolecularly, both chiral centers are R or bothchiral centers are S). Thus, the gelling agent contains less than about10%, preferably less than about 5%, more preferably less than about 2%,most preferably 0%, of the racemic form (R, S or S, R stereochemistrywithin the same molecule). It has been unexpectedly found that when anoptically enriched sample of gellant is used in the subject invention,superior gelling results. While not limited to any particular mechanismof action, it is believed that the optically enriched gellant isthermodynamically favored to form fibrils that are aligned and bundle,thereby contributing to a more ordered macrostructure in which theliquid base is trapped. The racemic mixture, on the other hand, isthermodynamically favored to form large crystals.

Mixtures of optically enriched gelling agents are also effective in thesubject invention.

The subject compositions preferably comprise from about 0.1% to about25%, more preferably from about 1% to about 15%, more preferably stillfrom about 3% to about 12%, most preferably from about 4% to about 10%of the gellant.

Liquid Base Material

The subject compositions also comprise a liquid base material. A liquidbase matrix is formed by combining the gelling agent with a liquid basematerial. As used herein, the term "liquid" refers to materials whichare liquids at ambient conditions and the term "liquid base material"includes all liquids within the composition.

The liquid base material of the subject invention is preferably used atlevels from about 10% to about 95% of the subject compositions; and morepreferably from about 45% to about 80%. The liquid base materialpreferably includes a volatile, non-polar, oil and a non-volatile,relatively polar co-solvent.

The term "non-polar" typically means that the solution has a solubilityparameter below about 6.5. The term "volatile" as used herein refers tomaterials which exhibit a vapor pressure of more than about 2 mm Hg at25° C. at one atmosphere and/or to materials which have a boiling pointat one atmosphere of at less than about 300° C. The non-polar, volatileoil tends to impart highly desirable aesthetic properties to the gel andis preferably used at levels from about 10% to about 70% of thecomposition; more preferably, from about 25% to about 60%; morepreferably from about 40%, to about 60%.

Particularly useful non-polar, volatile oils include silicone oils,hydrocarbons, and mixtures thereof. Such non-polar, volatile oils aredisclosed, for example, in Cosmetics, Science, and Technology, Vol. 1,27-104 edited by Balsam and Sagarin, 1972, incorporated herein byreference. The non-polar, volatile oils useful in the present inventionmay be saturated or unsaturated, straight or branched chained, aliphaticor aromatic. Preferred non-polar, volatile hydrocarbons includeisodecane (such as Permethyl-99A®, available from Presperse Inc.) andthe C₇ -C₈ through C₁₂ -C₁₅ isoparaffins (such as the Isopar® Seriesavailable from Exxon Chemicals).

Non-polar, volatile silicone oils are highly preferred because theyprovide the gel with highly desirable aesthetics. Non-polar, volatileliquid silicone oils are disclosed in U.S. Pat. No. 4,781,917 issued toLuebbe et al., on Nov. 1, 1988; and in Todd et al., "Volatile SiliconeFluids for Cosmetics", Cosmetics and Toiletries, 91:27-32 (1976); bothincorporated herein by reference. Particularly preferred volatilesilicone oils include cyclic volatile silicones corresponding to theformula: ##STR3## wherein n is from about 3 to about 7; and linearvolatile silicones corresponding to the formula:

    (CH.sub.3).sub.3 Si--O--[Si(CH.sub.3).sub.2 O].sub.m --Si(CH.sub.3).sub.3

wherein m is from about 1 to about 7. Linear volatile siliconesgenerally have a viscosity of less than about 5 centistokes at 25° C.,whereas the cyclic silicones have viscosities of less than about 10centistokes at 25° C. Highly preferred examples of volatile siliconeoils include cyclomethicones of varying viscosities, e.g., DowCorning200®, Dow Corning 244®, Dow Corning 245®, Dow Corning 344®, andDow Corning 345®, (commercially available from Dow Corning Corp.);SF-1204®and SF-1202® Silicone Fluids (commercially available from G. E.Silicones), GE 7207® and 7158® (commercially available from GeneralElectric Co.); and SWS-03314® (commercially available from SWS SiliconesCorp.).

The phrase "relatively polar" as used herein means more polar thananother material in terms of solubility parameter, i.e., the higher thesolubility parameter the more polar the liquid. The non-volatileco-solvent is "relatively polar" as compared to the non-polar, volatileoil discussed above. Therefore, the non-volatile co-solvent is morepolar (i.e., has a higher solubility parameter) than at least one of thenon-polar, volatile oils. The relatively polar co-solvent of the subjectinvention aids in the utilization of reduced processing temperatures bysolubilizing the gellant and being soluble in the non-polar, volatileoil when subjected to reduced processing temperatures. In addition toenabling reduced processing temperatures, the co-solvent enables theinclusion of greater amounts of the non-polar, volatile oil. This isadvantageous because, as discussed above, the non-polar, volatile oilprovides significant cosmetic benefits.

The quantity of relatively polar, non-volatile co-solvent is preferablykept to a minimum because it tends to adversely affect productcosmetics. The relatively polar, non-volatile co-solvent is preferablyincluded at levels from about 2% to about 60% of the composition; morepreferably from about 5% to about 25%; and most preferably from about 7%to about 20%.

Relatively polar, non-volatile liquids useful as the co-solvent in thesubject invention are disclosed, for example, in Cosmetics, Science, andTechnology, Vol. 1, 27-104 edited by Balsam and Sagarin, 1972; U.S. Pat.No. 4,202,879 issued to Shelton on May 13, 1980; and U.S. Pat. No.4,816,261 issued to Luebbe et al. on Mar. 28, 1989; all incorporatedherein by reference. Relatively polar, non-volatile co-solvents usefulin the subject invention preferably include silicone oils; hydrocarbonoils; fatty alcohols; fatty acids; esters of mono and dibasic carboxylicacids with mono and polyhydric alcohols; polyoxyethylenes;polyoxypropylenes; mixtures of polyoxyethylene and polyoxypropyleneethers of fatty alcohols; and mixtures thereof. The relatively polar,non-volatile co-solvents useful in the subject invention may be eithersaturated or unsaturated, have an aliphatic character and be straight orbranched chained or contain aliphatic rings or aromatic rings.

More preferably, the relatively polar, non-volatile liquid co-solventsinclude fatty alcohols having from about 12-26 carbon atoms; fatty acidshaving from about 12-26 carbon atoms; esters of monobasic carboxylicadds and alcohols having from about 14-30 carbon atoms; esters ofdibasic carboxylic acids and alcohols having from about 10-30 carbonatoms; esters of polyhydric alcohols and carboxylic acids having fromabout 5-26 carbon atoms; ethoxylated, propoxylated, and mixtures ofethoxylated and propoxylated ethers of fatty alcohols with from about12-26 carbon atoms and a degree of ethoxylation and propoxylation ofbelow about 50; and mixtures thereof.

More preferred relatively polar, non-volatile liquid co-solvents includepropoxylated ethers of C₁₄ -C₁₈ fatty alcohols having a degree ofpropoxylation below about 50, esters of C₂ -C₈ alcohols and C₁₂ -C₂₆carboxylic acids (e.g. ethyl myristate, isopropyl palmitate), esters ofC₁₂ -C₂₆ alcohols and benzoic acid (e.g. Finsolv TN supplied byFinetex), diesters of C₂ -C₈ alcohols and adipic, sebacic, and phthalicacids (e.g., diisopropyl sebacate, diisopropyl adipate, di-n-butylphthalate), polyhydric alcohol esters of C₆ -C₂₆ carboxylic acids (e.g.,propylene glycol dicaprate/dicaprylate, propylene glycol isostearate);and mixtures thereof.

Even more preferred relatively polar, non-volatile liquid co-solventsinclude branched-chain aliphatic fatty alcohols having from about 12-26carbon atoms, such as isocetyl alcohol, octyldecanol, octyldodecanol andundecylpentadecanol. Octyldodecanol is most preferred. Such preferredaliphatic fatty alcohols are particularly useful in combination with thevolatile liquid silicone oils discussed herein to adjust the averagesolubility of the liquid base material.

In addition to the liquids discussed above, the liquid base material mayoptionally include non-volatile, non-polar emollients which tend toimprove product cosmetics. Typical non-volatile, non-polar emollientsare disclosed, for example, in Cosmetics, Science, and Technology, Vol.1, 27-104 edited by Balsam and Sagarin, 1972; U.S. Pat. No. 4,202,1379issued to Shelton on May 13, 1980; and U.S. Pat. No. 4,816,261 issued toLuebbe et al. on Mar. 28, 1989; all incorporated herein by reference.The non-volatile silicone oils useful in the present invention areessentially non-volatile polysiloxanes, paraffinic hydrocarbon oils, andmixtures thereof. The polysiloxanes useful in the subject inventioninclude polyalkylsiloxanes, polyarylsiloxanes, polyalkylarylsiloxanes,polyethersiloxane copolymers, and mixtures thereof. Examples of theseinclude polydimethyl siloxanes having viscosities of from about 5 toabout 100,000 centistokes at 25° C.

Among the preferred non-volatile silicone emollients useful in thesubject compositions are the polydimethyl siloxanes having viscositiesfrom about 2 to about 400 centistokes at 25° C. Such polyalkylsiloxanesinclude the Viscasil® series (sold by General Electric Company) and theDow Corning 200® series (sold by Dow Corning Corp.).Polyalkylarylsiloxanes include polymethylphenyl siloxanes havingviscosities of from about 15 to about 65 centistokes at 25° C. These areavailable, for example, as SF 1075 methyl-phenyl fluid® (sold by GeneralElectric Company) and 556 Cosmetic Grade Fluid® (sold by Dow CorningCorp.). Useful poly-ethersiloxane copolymers include, for example, apolyoxyalkylene ether copolymer having a viscosity of about 1200 to 1500centistokes at 25° C. Such a fluid is available as SF1066®organosilicone surfactant (sold by General Electric Company).Polysiloxane ethylene glycol ether copolymers are preferred copolymersfor use in the subject compositions.

Non-volatile paraffinic hydrocarbon oils useful in the subject inventioninclude mineral oils and certain branched-chain hydrocarbons. Examplesof these fluids are disclosed in U.S. Pat. No. 5,019,375 issued toTanner et al. on May 28, 1991, incorporated herein by reference.Preferred mineral oils have the following properties: viscosity fromabout 5 centistokes to about 70 centistokes at 40° C.; density betweenabout 0.82 and 0.89 g/cm³ at 25° C.; flash point between about 138° C.and about 216° C.; and carbon chain length between about 14 and about 40carbon atoms.

Preferred branched chain hydrocarbon oils have the following properties:density between about 0.79 and about 0.89 g/cm³ at 20° C.; boiling pointgreater than about 250° C.; and flash point between about 110° C. andabout 200° C.

Particularly preferred branched-chain hydrocarbons include Permethyl103A®, which contains an average or about 24 carbon atoms; Permethyl104A®, which contains an average of about 68 carbon atoms; Permethyl102A®, which contains an average of about 20 carbon atoms; all of whichmay be purchased from Permethyl Corporation; and Ethylflo 364® whichcontains a mixture of 30 carbon atoms and 40 carbon atoms and may bepurchased from Ethyl Corp.

The liquid base materials include emollients which have a solubilityparameter from about 5 to about 9. It is preferable that, in aggregate,the average solubility parameter of the liquid base material be fromabout 6 to about 9. Hence, a mixture of emollients may be used as theliquid base material herein, each having a solubility parameter in therange of from about 5 to about 9, such that the average solubilityparameter of the mixture is from about 6 to about 9. Solubilityparameters are common to the art of antiperspirant stick formulation andthe means to determine them are disclosed by C. D. Vaughan, "SolubilityEffects in Product, Package, Penetration and Preservation" 103 Cosmeticsand Toiletries 47-69, October 1988; and C. D. Vaughan, "Using SolubilityParameters in Cosmetics Formulation", 36 J Soc. Cosmetic Chemists319-333, September/October, 1985; both incorporated herein by reference.

The liquid base material comprises at least two solvents. One solvent ispreferably a silicone oil. The second solvent is preferably an organicsolvent with a solubility parameter of less than 9.

It is important that the liquid base material be of a type, and used ata level sufficient to solubilize the gelling agent when heated, topermit substantially uniform mixing. The liquid base material must becompatible with the gelling agent so that the mixture of the two remainshomogeneous and does not phase separate during manufacturing and so thatthe finished product remains homogeneous and does not phase separate atambient conditions over the normal shelf-life which may be upwards ofone year. Furthermore, the liquid base materials are typically selectedto provide aesthetic benefits, such as emolliency, low tack and/orminimized visible residue, without significant interference with othercomponents of the formulation. The particular liquid base materialshould be safe for application to human skin.

As used herein, the term "gel" means a non free flowing solid after thegellant has been melted and allowed to cool to ambient temperature.

As used herein, the term "low-aqueous gel composition" means a gelcomposition comprising less than 50% water, preferably less than 30%,more preferably less than 20% water, even more preferably less than 10%water, also preferably less than 5% water. The most preferred gelcompositions are substantially water free. As used herein, the term"substantially water free" means that the only water content in theformulation comes from the degrees of hydration associated with the rawmaterials used in the formulation.

Optional Ingredients

Gel compositions of the subject invention may contain optionalcomponents which act as additional actives or modify the physicalcharacteristics of the composition or the components making up thecompositions. Such components are well known in the art. A non-limitinggroup of these optional components include colorants, perfumes,thickeners, distributing agents, emulsifiers, bacteriostats, fungistats,and mixtures thereof. Optional components useful herein are described inthe following references: U.S. Pat. No. 4,049,792 issued to Elsnau onSep. 20, 1977; Canadian Patent 1,164,347 which issued to Beckmeyer etal. on Mar. 27, 1984; European Patent Application 117,070 whichpublished on Aug. 29, 1984; and Geria, "Formulation of StickAntiperspirants and Deodorants", Cosmetics and Toiletries, 99:55-60(1984); all incorporated herein by reference.

Emulsifiers are particularly useful in the subject invention. The levelof emulsifiers used in the subject invention is typically less thanabout 10% of the composition, preferably less than about 5%. Theseemulsifiers include non-ionic surfactants useful for formingwater-in-oil emulsions. Examples of these emulsifiers includepolyoxyethylene ethers of fatty alcohols, andpolyoxyethylene-polysiloxane copolymers. Such emulsifiers are disclosedby EPO Application 373,424 Raleigh et al., and U.S. Ser. No. 530,671,Cedeno et al., filed Jul. 2, 1991; incorporated herein by reference.

Thickeners are also useful in the subject invention. Typically,thickeners comprise less than about 5% of the composition. Examples ofthickeners useful in the subject compositions are disclosed in U.S. Pat.No. 4,985,238, Tanner et al., issued Jan. 15, 1991; incorporated hereinby reference. These thickeners include wax-like materials such asbeeswax, cerasin, hydrogenated castor oil, synthetic waxes such asFisher Tropsch® waxes, microcrystalline waxes, polyethylene waxes, andmixtures thereof. Particulate thickeners, such as clay and silica, arealso useful.

Particulate and filler materials may also be included in the subjectcompositions. These materials are typically used at levels from about0.5% to about 5% of the composition, preferably not more than 3%. Suchmaterials are disclosed in U.S. Pat. No. 5,019,375, Tanner et al.,issued May 28, 1991; incorporated herein by reference. Suitable fillermaterials include collodial silica (such as Cab-O-Sil®, sold by CabotCorp.), clays (such as bentonite), hydrophobic (quaternized) clays,silica/alumina thickeners, silicate powders such as talc, aluminasilicate, and magnesium silicate, modified corn starches, metallicstearates, and mixtures thereof. The use of such fillers as stabilizingagents in cosmetic sticks is disclosed in U.S. Pat. No. 4,126,679, Davyet al., issued Nov. 21, 1987; incorporated herein by reference. Examplesof other particulate materials include particulate hydrophilic polymerssuch as cellulose ether polymers, modified starches, polyamides, andpolypeptides.

A wash-off agent may be utilized to improve the ease with which theingredients, particularly the gelling agent and the non-polar,non-volatile oils, may be washed off. The wash-off agent is preferably anon-liquid. The wash-off agent is typically in the gel in an amount fromabout 0.1% to about 10% of the composition.

Typical wash-off agents are non-liquids selected from the groupconsisting of polyoxyethylene ethers having the formula R₁ (OCH₂CH₂)_(n) OH; polyoxyethylene esters having the formula R₁ CO(OCH₂CH₂)_(n) OH; polyoxyethylene glyceryl esters having the formula (R₁COO)CH₂ CH(OH)CH₂ (OCH₂ CH₂)_(n) OH or having the formula HOCH₂CH(OOCR₁)CH₂ (OCH₂ CH₂)_(n) OH; and polyoxyethylene glyceryl diestershaving the formula R₁ COOCH₂ CH(OOCR₂)CH₂ (OCH₂ CH₂)_(n) OH, preferably,the polyoxyethylene ethers, wherein R₁ and R₂ are, independently, alkyl,alkenyl, or aromatic hydrocarbon which may be substituted orunsubstituted, preferably an alkyl radical, having from about 4 to about22 carbon atoms; and n is from about 2 to about 80.

Preferred examples of such wash-off agents include: ceteth-2 throughceteth-30, steareth-2 through steareth-30, ceteareth-2 throughceteareth-30, PEG-2 stearate through PEG-30 stearate, PEG-12isostearate, PEG-16 hydrogenated castor oil, PEG-40 hydrogenated castoroil, Unithox-480®, Unithox-425®, and PEG-20 glyceryl stearate; morepreferably, ceteareth-20, steareth-21, PEG-20 stearate, Unithox-480®,Unithox-425®, and PEG-16 hydrogenated castor oil; more preferably still,ceteareth-20, Unithox-480® and Unithox-425®; also preferablyUnithox-480® and Unithox-425®.

Antiperspirants

The subject gels are particularly useful for antiperspirant and/ordeodorant compositions. Such compositions contain an astringentantiperspirant active. Antiperspirant actives useful in the subjectinvention are well known in the art. See e.g. "Antiperspirants andDeodorants", Cosmetic Science and Technology Series, K. Laden & C.Felger, eds., Vol. 7., pp. 42-56 (1988); incorporated herein byreference. These actives are used at levels from about 0.5% to about 60%of the composition, preferably from about 5% to about 35%, of the gelstick composition. These weight percentages are calculated on ananhydrous metal salt basis (exclusive of complexing agents).

Any aluminum astringent antiperspirant salt or aluminum and/or zirconiumastringent complex can be employed herein. Salts useful as astringentantiperspirant salts or as components of astringent complexes includealuminum halides, aluminum hydroxy-halides, zirconyl oxyhalides,zirconyl hydroxy-halides, and mixtures of these materials.

Aluminum salts of this type include aluminum chloride and the aluminumhydroxyhalides having the general formula Al₂ (OH)_(x) Q_(y).XH₂ Owherein:

(a) Q is chlorine, bromine or iodine;

(b) x is from about 2 to about 5, and x+y=about 6, and x and y do notneed to be integers; and

(c) X is from about 1 to about 6.

Aluminum salts of this type can be prepared in the manner described morefully in U.S. Pat. No. 3,887,692 issued to Gilman on Jun. 3, 1975, andU.S. Pat. No. 3,904,741 issued to Jones and Rubino on Sep. 9, 1975; bothincorporated herein by reference.

The zirconium compounds which are useful in the present inventioninclude both the zirconium oxy salts and zirconium hydroxy salts, alsoreferred to as the zirconyl salts and zirconyl hydroxy salts. Thesecompounds may be represented by the following general empirical formula:

    ZrO(OH).sub.2-nz B.sub.z

wherein:

(a) z may vary from about 0.9 to about 2 and need not be an integer,

(b) n is the valence of B;

(c) 2-nz is greater than or equal to 0:

(d) B is selected from the group consisting of halides, nitrate,sulfamate, sulfate, and mixtures thereof.

Although only zirconium compounds are exemplified in this specification,other Group IVB metal compounds, including hafnium, can be used in thesubject invention.

As with the basic aluminum compounds, the above formula is greatlysimplified and is intended to represent and include compounds havingcoordinated and/or bound water in various quantities, as well aspolymers, mixtures and complexes of the above. As will be seen from theabove formula, the zirconium hydroxy salts actually represent a range ofcompounds having various amounts of the hydroxy group, varying fromabout 1.1 to only slightly greater than zero groups per molecule.

Several types of antiperspirant complexes utilizing the aboveantiperspirant salts are known in the art. For example, U.S. Pat. No.3,792,068 issued to Luedders et al. on Feb. 12, 1974 discloses complexesof aluminum, zirconium and amino acids, such as glycine. Complexes suchas those disclosed in the Luedders et al. patent and other similarcomplexes are commonly known as ZAG. ZAG complexes are chemicallyanalyzable for the presence of aluminum, zirconium and chlorine. ZAGcomplexes useful herein are identified by the specification of both themolar ratio of aluminum to zirconium (hereinafter "Al:Zr" ratio) and themolar ratio of total metal to chlorine (hereinafter "Metal:Cl" ratio).ZAG complexes useful herein have an Al:Zr ratio of from about 1.67 toabout 12.5 and a Metal:Cl ratio of from about 0.73 to about 1.93.

Preferred ZAG complexes are formed by

(A) co-dissolving in water

(1) one part Al₂ (OH)_(6-m) Q_(m), wherein Q is an anion selected fromthe group consisting of chloride, bromide and iodide, and m is a numberfrom about 0.8 to about 2.0;

(2) x parts ZrO(OH)_(2-a) Q_(a).nH₂ O, where Q is chloride, bromide oriodide; where a is from about 1 to about 2; where n is from about 1 toabout 8; and where x has a value of from about 0.16 to about 1.2;

(3) p parts neutral amino acid selected from the group consisting ofglycine, dl-tryptophane, dl-b-phenylalanint, dl-valine, dl-methionineand b-alanine, and where p has a value of from about 0.06 to about 0.53;

(B) co-drying the resultant mixture to a friable solid; and

(C) reducing the resultant dried inorganic-organic antiperspirantcomplex to particulate form.

A preferred aluminum compound for preparation of such ZAG type complexesis aluminum chlorhydroxide of the empirical formula Al₂ (OH)₅ Cl.2H₂ O.Preferred zirconium compounds for preparation of such ZAG-type complexesare zirconyl hydroxychloride having the empirical formula ZrO(OH)Cl.3H₂O and the zirconyl hydroxyhalides of the empirical formula ZrO(OH)_(2-a)Cl₂ nH₂ O wherein a is from about 1.5 to about 1.87, and n is from about1 to about 7. The preferred amino acid for preparing such ZAG-typecomplexes is glycine of the formula CH₂ (NH₂)COOH. Salts of such aminoacids can also be employed in the antiperspirant complexes. See U.S.Pat. No. 4,017,599 issued Apr. 12, 1977, to Rubino; incorporated hereinby reference.

A wide variety of other types of antiperspirant complexes are also knownin the art. For example, U.S. Pat. No. 3,903,258 issued to Siegal onSep. 2, 1975 discloses a zirconium aluminum complex prepared by reactingzirconyl chloride with aluminum hydroxide and aluminum chlorhydroxide.U.S. Pat. No. 3,979,510 issued to Rubino on Sep. 7, 1976 discloses anantiperspirant complex formed from certain aluminum compounds, certainzirconium compounds, and certain complex aluminum buffers. U.S. Pat. No.3,981,896 issued to Pauling on Sep. 21, 1976 discloses an antiperspirantcomplex prepared from an aluminum polyol compound, a zirconium compoundand an organic buffer. U.S. Pat. No. 3,970,748 issued to Mecca on Jul.20, 1976 discloses an aluminum chlorhydroxy glycinate complex of theapproximate general formula [Al₂ (OH)₄ Cl][H₂ CNH₂ COOH].

Of all the above types of antiperspirant actives, preferred compoundsinclude the 5/6 basic aluminum salts of the empirical formula Al₂ (OH)₅Cl.2H₂ O; mixtures of AlCl₃.6H₂ O and Al₂ (OH)₅ Cl.2H₂ O with aluminumchloride to aluminum hydroxychloride weight ratios of up to about 0.5;ZAG type complexes wherein the zirconium salt is ZrO(OH)Cl.3H₂ O, thealuminum salt is Al₂ (OH)₅ Cl.2H₂ O or the aforementioned mixtures ofAlCl₃.6H₂ O and Al₂ (OH)₅ Cl.2H₂ O wherein the total metal to chloridemolar ratio in the complex is less than about 1.25 and the Al:Zr molarratio is about 3.3, and the amino acid is glycine; and ZAG-typecomplexes wherein the zirconium salt is ZrO(OH)_(2-a) Cl_(a).nH₂ Owherein a is from about 1.5 to about 1.87 and n is from about 1 to about7, the aluminum salt is Al₂ (OH)₅ Cl.2H₂ O, and the amino acid isglycine.

The active may be incorporated either in solubilized or particulateform. Reduction in the amount of interaction between the antiperspirantactive and the gelling agent results in better gel stick compositions.This interaction can he reduced by decreasing the surface area of theantiperspirant active; thereby reducing the interaction sites. Theantiperspirant active is preferably in particulate form wherein thesurface area of the active is relatively low. The surface area of theantiperspirant active can be reduced by increasing the size and densityof the active particles. The particulate antiperspirant activepreferably has a density which is greater than about 0.7 g/cm³ and anaverage particle size (as measured by a Coulter Multisizer 11manufactured by Coulter Corporation, Haleah, Fla.) greater than about 10microns; more preferably, greater than about 30 microns; and mostpreferably, greater than about 40 microns. Such preferred materials canbe purchased from Westwood Chemical Company, Middletown, N.Y. under thetrade name Westchlor ZR. Suitable antiperspirant actives are disclosed,for example, in U.S. Pat. No. 4,147,766 which issued on Apr. 3, 1979 toKozischek.

Solubilized antiperspirant actives which may be utilized in the subjectinvention are also well known in the art. These materials utilizemonohydric or polyhydric alcohols or water to solublize theantiperspirant active before it is incorporated into the product. Thelevels of these polar solvents is less than 25%, and preferably lessthan 15% of the composition. Examples of such actives are taught, forexample, in U.S. Pat. No. 4,137,306 issued to Rubino on Jan. 30, 1979;U.S. patent application Ser. No. 370,559, Smith and Ward, filed Jun. 23,1989; and European Patent Application 0295070 published Dec. 14, 1988;all incorporated herein by reference.

METHODS OF MANUFACTURE

The subject compositions may be manufactured by typical methods known tothose skilled in the art. See, e.g., Gels and Sticks Formulary, 99Cosmetics & Toiletties 77-84, 1984; incorporated herein by reference.The following method is particularly preferred.

The gelling agent and the liquid base material are combined in a vesselequipped with a heat source. The mixture is heated to between about 80°C. and about 140° C. with stirring until a homogeneous, molten solutionis formed. Preferably, the homogeneous, molten solution is allowed tocool to a mixing temperature, typically between about 65° C. and about120° C. Alternatively, the mixture is heated to the mixing temperatureuntil the mixture forms a homogeneous, molten solution. This alternativemethod, however, typically takes longer than overheating and cooling.

In case of antiperspirants, the active and optional ingredients, such asfragrances and colors, are added into the homogeneous molten solution inthe above vessel with stirring. The mixture is cooled until thickeningoccurs and poured into containers.

EXAMPLES

The following examples further describe and demonstrate embodimentswithin the scope of the subject invention. These examples are solely forthe purpose of illustration and are not to be construed as limitationsof the present invention as many variations are possible withoutdeparting from the spirit or scope thereof.

The levels of the components in the examples below are expressed bytotal weight of the composition.

    __________________________________________________________________________    weight of the composition.                                                                  EXAMPLE NO.                                                     Ingredient    1   2  3    4  5    6  7    8                                   __________________________________________________________________________    11,12 di-hydroxystearic acid                                                                --  2  1    5  7    -- 6    --                                  (S,S isomer)                                                                  11,12 di-hydroxystearic acid                                                                2   3  4    1  --   3  --   1                                   (R,R isomer)                                                                  Cyclomethicone D-5.sup.1                                                                    q.s.                                                                              q.s.                                                                             q.s. q.s.                                                                             q.s. q.s.                                                                             q.s. q.s.                                Polyphenylmethyl-                                                                           --  -- --   3  --   -- 5    --                                  siloxane.sup.2                                                                Light mineral oil.sup.3                                                                     2   -- --   -- --   -- --   --                                  Panalane-L-14E ®.sup.4                                                                  --  15 10   11 --   -- --   --                                  Isopropyl Myristate                                                                         --  15 15   16 --   -- 11   --                                  Isopropyl Alcohol                                                                           --  -- --   -- 18   -- --   --                                  Captex 200 ®.sup.5                                                                      --  -- --   -- --   15 --   --                                  C.sub.12 -C.sub.15 Alcohols                                                                 --  -- --   -- --   -- 8    --                                  Benzoate.sup.6                                                                PPG-3 Myristyl Ether                                                                        --  -- --   -- --   -- --   26                                  Diisopropyl Sebacate.sup.7                                                                  43  -- --   -- --   -- --   --                                  Aluminum Zirconium                                                                          25  -- --   20 --   40 25   --                                  Trichlorhydrex Gly ®.sup.8                                                Aluminum Chlorohydrate.sup.9                                                                --  -- --   -- 30   -- --   --                                  EDTA          0.2 0.1                                                                              0.5  1  5    10 7    0.01                                Talc          3   -- --   2  --   -- --   5                                   __________________________________________________________________________     .sup.1 Dow Corning 245 Fluid cyclic polydimethylsiloxane                      .sup.2 Dow Corning 556 Fluid                                                  .sup.3 Benol White Mineral Oil supplied by Witco Chemical Corp.               .sup.4 polyisobutene supplied by Amoco Chemical Company                       .sup.5 propylene glycol dicaprate/dicaprylate supplied by Capital City        Products                                                                      .sup.6 Finsolv TN ® supplied by Finetex                                   .sup.7 Schercemol DIS ® supplied by Scher Chemicals Inc.                  .sup.8 Supplied by Westwood Chemical Co.                                      .sup.9 Westchlor DM200 ® supplied by Westwood Chemical Co.           

    EXAMPLE NO.                                                                   Ingredient     9  10 11 12 13 14 15 16 17 18                                  __________________________________________________________________________    13,14-dihydroxydocosanoic acid                                                               6  6  6  6  6  6  6  6  6  6                                   (S,S isomer)                                                                  Cyclomethicone D4.sup.1                                                                      q.s.                                                                             -- q.s.                                                                             -- q.s.                                                                             q.s.                                                                             q.s.                                                                             q.s.                                                                             -- --                                  Cyclomethicone D-5.sup.2                                                                     -- q.s.                                                                             -- q.s.                                                                             -- -- -- -- q.s.                                                                             q.s.                                PPG-3-myristyl ether                                                                         -- -- -- -- -- 12 -- -- -- --                                  PPG-5-butyl ether                                                                            -- -- -- -- -- -- 10.5                                                                             -- -- --                                  PPG-10-cetyl ether                                                                           -- -- -- -- -- -- -- 12.5                                                                             -- --                                  Isocetyl alcohol                                                                             7  8  13 -- -- -- -- -- -- --                                  Isostearyl alcohol                                                                           -- -- -- 13 -- -- -- -- -- --                                  Octyldodecanol -- -- -- -- 8.5                                                                              -- -- -- 14 14                                  Polydecene.sup.3                                                                             -- -- 26 -- -- -- -- -- -- --                                  Citric Acid    4  1  10 0.1                                                                              2  5  0.2                                                                              0.5                                                                              0.01                                                                             0.05                                Ceteareth-20   -- -- -- -- -- -- -- -- 2.5                                                                              2.5                                 Dipropyleneglycol                                                                            -- -- -- -- -- -- -- -- -- 0.25                                C.sub.20-40 alcohols.sup.4                                                                   -- -- -- -- -- -- -- -- 0.5                                                                              0.5                                 __________________________________________________________________________     .sup.1 Dow Corning 245 Fluid ® cyclic polydimethylsiloxane                .sup.2 Dow Corning 244 Fluid ® cyclic polydimethylsiloxane                .sup.3 Ethylflo 364 ® supplied by Ethyl Corp.                             .sup.4 Unilin 425 ® supplied by Petrolite                            

    Ingredient             EXAMPLE 19                                             __________________________________________________________________________    Octyldodecanol         14                                                     6,7 dihydroxystearic acid (S,S isomer)                                                               7                                                      Unithox 480 ®      1.25                                                   Unithox 425 ®      0.5                                                    Aluminum Zirconium Trichlorohydrex Gly ®.sup.1                                                   26                                                     Cyclomethicone D-5.sup.2                                                                             q.s.                                                   __________________________________________________________________________     .sup.1 Supplied by Westwood Chemical Co.                                      .sup.2 Dow Corning 245 Fluid ® cyclic polydimethylsiloxane           

    Ingredient              EXAMPLE 20                                                                            EXAMPLE 21                                    __________________________________________________________________________    C.sub.12 -C.sub.15 Alcohols Benzoate (Finsolv TN ®)                                               30      30                                            Cyclomethicone D-5      q.s.    q.s.                                          11,12 dihydroxystearic acid (S,S isomer)                                                              10      10                                            Aluminum Zirconium Trichlorohydrex Gly ®                                                          26      --                                            __________________________________________________________________________    Ingredient            EXAMPLE 22                                              __________________________________________________________________________    13,14-dihydroxydocosanoic acid (R,R isomer)                                                         5                                                       Triclosan             0.3                                                     Perfume               0.1                                                     Cyclomethicone D-5    q.s.                                                    C.sub.12 -C.sub.15 Alcohols Benzoate (Finsolv TN ®)                                             33.1                                                    __________________________________________________________________________    Ingredient           EXAMPLE 23                                               __________________________________________________________________________    11,12-dihydroxystearic acid (R,R isomer)                                                           4                                                        9,10-dihydroxystearic acid (R,R isomer)                                                            1                                                        Triclosan            0.3                                                      Perfume              0.1                                                      Cyclomethicone D-5   q.s.                                                     C.sub.12 -C.sub.15 Alcohols Benzoate (Finsolv TN ®)                                            33.1                                                     __________________________________________________________________________

What is claimed is:
 1. A low-aqueous antiperspirant gel compositioncomprising:a) an effective amount of an antiperspirant active; b) asufficient amount of an optically enriched gellant to form a gel whereinsaid gellant has the structure: ##STR4## wherein A and B independentlyrepresent linear, branched or cyclic, saturated or unsaturated,substituted or unsubstituted alkyl groups wherein the substituents areselected from the group consisting of halogen, hydroxyl, amino, nitro,carboxy, thio aryl, alkyl, alkoxy, aryloxy groups and mixtures thereof,such that the gellant is an asymmetric, di-chiral, di-hydroxy fatty acidthat is about 90% or more in the R, R or S, S form and has from about 6to about 30 carbon atoms; and c) a sufficient amount of a liquid basematerial, liquid at ambient conditions, selected from the groupconsisting of volatile and non-polar oils, non-volatile and relativelypolar co-solvents and mixtures thereof.
 2. The composition of claim 1wherein:a) A and B each represent linear or branched alkyl having fromabout 3 to about 12 carbon atoms; b) the gellant has from about 10 toabout 28 carbon atoms and is about 95% or more in the R, R or S, S form;and c) the active is a complex of aluminum, zirconia and amino acids. 3.The composition of claim 2 wherein A and B represent unsubstituted alkylor substituted alkyl wherein any substituent is selected from the groupconsisting of halogen, hydroxy, amino, nitro, carboxy, thio, akyl,alkyl, alkoxy and aryloxy.
 4. The composition of claim 3 wherein A and Beach represent linear, saturated alkyl which are unsubstituted orsubstituted, any substituent being selected from the group consisting ofalkyl, alkoxy and aryl.
 5. The composition of claim 4 wherein thecomposition is substantially water free and is about 98% or more in theR, R or S, S form.
 6. The composition of claim 5 wherein the liquid basematerial comprises at least two solvents.
 7. The composition of claim 6wherein the gellant has about 22 carbon atoms, and is about 100% in theR, R or S, S form.